Preparation method for solid powder of a carbamic acid derivative

ABSTRACT

The present application relates to a preparation method for solid powder of a carbamic acid derivative, which includes reacting an amine derivative with carbon dioxide at a temperature in a range of from about −30° C. to about 500° C. and at a pressure in a range of from about 0.3 MPa to about 100 MPa. In addition, the present disclosure relates to a reduction method for solid powder of a carbamic acid derivative to an amine derivative and carbon dioxide, which includes dissolving solid powder of the carbamic acid derivative prepared in a solvent; refluxing the carbamic acid derivative at a temperature in a range of from about 30° C. to about 100° C.; and evaporating the solvent.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent applicationSer. No. 13/967,036 filed on Aug. 14, 2013 which is a continuation ofInternational Application No. PCT/KR2012/001046 filed on Feb. 13, 2012,claiming the priority based on Korean Patent Application No.10-2011-0012972 filed on Feb. 14, 2011.

TECHNICAL FIELD

The embodiments described herein pertain generally to a preparationmethod for solid powder of a carbamic acid derivative and a reductionmethod for the solid powder of a carbamic acid derivative, and morespecifically, to a preparation method for the solid powder of thecarbamic acid derivative through a reaction between an amine derivativewith carbon dioxide, and a reduction method for the solid powder of thecarbamic acid derivative to the amine derivative and the carbon dioxide.

BACKGROUND

An amine compound refers to a compound, such as an ammonia molecule,containing a nitrogen atom having an unshared electron pair and istypically basic. Such an amine compound has been found from both plantsand animals. Amine compounds extracted from plants include nicotinecontained in tobacco and cocaine which can cause hallucination. Many ofdaily used drugs contain an amine functional group. A typical drug ispenicillin. Further, dopamine well known as a material that stimulatesbrain nerves and phenylethylamine as a main substance of chocolate aretypical compounds each containing an amine functional group. In manycases, amine compounds each having a relatively small molecular weightexist in a liquid-phase form at room temperature under atmosphericpressure, give out smell of fish, and cause skin allergies. Further,such liquid amines easily react with oxygen or the like in the air so asto be changed, and, thus, if they are not completely sealed, it isdifficult to maintain purity thereof. Therefore, liquid amines aredifficult to handle and store and are limited in applications thereof.

As a method for solving the above problem, a solid amine salt preparedby reacting an amine with an acid has been used in substitution foramine. Such an amine salt is prepared as a solid salt by adding a strongacid such as sulfuric acid or hydrochloric acid to a liquid amine with aprecipitation reaction. By way of example, when a hydrochloric acidsolution is put into phenylethylamine, a precipitation reaction occursin an instant with conversion into phenylethylamine hydrochloric acidwhich has been actually used in substitution for liquid amine. Suchsolid amine salts exist in a stable solid form at room temperature andhave characteristics similar to those of liquid amines when they aredispersed in a solution and react with other compounds. Further, suchsalts have a very high solubility to water and are useful for utilizingamine. In particular, a drug containing an amine functional group whichis not dissolved well in water due to its high molecular weight is usedas being bonded to an acid such as hydrochloric acid. This is because ifthe drug is converted into a salt, solubility is sharply increased in anaqueous solution and thus the drug is suitable for use as a drug.

However, such amine salts need a solvent when being generated, thesolvent needs to be removed after a reaction due to unnecessarymaterials added to generate the salts, and an additional process forremoving a remaining material is needed. Further, a neutralizationprocess for removing a strong acid such as hydrochloric acid or sulfuricacid used in a process for preparing an amine salt is essential. Such amultistep process causes environmental pollution.

As described above, as one of alternatives to solve such problems of theliquid amine and the solid amine salt, there is a method for preparingsolid amine derivatives from a liquid amine by using eco-friendly carbondioxide as a reactant. If a reaction is made between a liquid amine andcarbon dioxide, the carbon dioxide is generally inserted into N—H bondsof amine molecules and converted into carbamic acid derivatives. Most ofthese carbamic acid derivatives exist in a stable solid form in the air.Further, they can be easily separated into the amine and the carbondioxide by a slight external change, and, thus, they can act as a goodalternative to solve the problems of the liquid amine and the solidamine salt.

Many methods for preparing new compounds using carbon dioxide as areactant have been known so far, and various methods for preparing newcompounds by the methods have been reported [Sakakura, T.; Choi, J.-C.;Yasyda, H., Chem. Rev., 2007, 107, 2365]. Further, it is known thatcarbamic acid derivatives can be formed by a reaction between an amineand carbon dioxide. However, in most of the conventionally knownreactions between an amine and carbon dioxide, while carbon dioxide gasis discharged under atmospheric pressure for a long time by using asolvent, a compound is formed in a reactor and used, without anadditional separation process, for an intermediate step in a process forforming another compound, or a compound is used for synthesizing acompound in a gel form (U.S. Pat. No. 3,551,226), or there are knownresearches in which a compound is formed by using a polar solvent as anionic liquid [1) Jessop, P. G.; Heldebrant, D. J.; Li, X.; Eckert, C.A.; Liotta, C. L., Nature, 2005, 436, 1102, 2) Lam Phan; Andreatta J.R.; Horvey, L. K.; Edie, C. F.; Luco. Aimé e-L.; Mirchandani, A.;Darensbourg, D. J.; Jessop, P. G., J. Org. Chem., 2008, 73, 127-132, 3)Liu, Y.; Tang, Y.; Barashkov, N. N.; Irgibaeva, I. S.; Y. Lam, J.; Hu,W. R.; Birimzhanova, D.; Yu, Y.; Tang, B. Z., J. Am. Chem. Soc., 2010,132, 13951].

In U.S. Pat. No. 3,551,226, it is disclosed that liquid amines reactwith carbon dioxide under atmospheric pressure at a low temperature fora long time and are converted into and used as a gel type compound. Sucha gel type compound contains amine and carbon dioxide at an irregularratio and is a very sticky liquid, and, thus, it is difficult toseparate the gel type compound into a pure solid amine in powder form bya typical drying method. Further, if an amine is solidified by usingcarbon dioxide under atmospheric pressure, a sticky gel type compound isobtained rather than a solid compound powder. As described above, it isknown that carbamic acid derivatives can be formed by a reaction betweenan amine and carbon dioxide. However, there is no research resultregarding a separation or preparation method for a solid carbamic acidderivative in powder form.

SUMMARY

In order to solve problems of an amine derivative in a liquid form atroom temperature under atmospheric pressure, an objective of the presentdisclosure is to provide a preparation method for a carbamic acidderivative in solid powder form from a liquid amine derivative by usingcarbon dioxide as a reactant.

Further, another objective of the present disclosure is to provide areduction method for the solid powder of the carbamic acid derivative tothe liquid amine derivative and the carbon dioxide.

However, the problems sought to be solved by the present disclosure arenot limited to the above description and other problems can be clearlyunderstood by those skilled in the art from the following description.

In accordance with an aspect of the present disclosure, there isprovided a preparation method for solid powder of a carbamic acidderivative, including: reacting an amine derivative with carbon dioxideat a temperature in a range of from about −30° C. to about 500° C. andat a pressure in a range of from about 0.3 MPa to about 100 MPa.

In accordance with another aspect of the present disclosure, there isprovided a reduction method for solid powder of a carbamic acidderivative to an amine derivative and carbon dioxide, including:dissolving the solid powder of the carbamic acid derivative prepared bythe preparation method of the present disclosure in a solvent; refluxingthe carbamic acid derivative in the solvent at a temperature in a rangeof from about 30° C. to about 100° C.; and evaporating the solvent.

According to an example embodiment of the present disclosure, in apreparation method for solid powder of a carbamic acid derivative, anamine and carbon dioxide react with each other at a high pressurewithout using a solvent, and, thus, they can be easily converted intopure solid powder of a carbamic acid derivative without by-products, andtime and energy required for solidification can be remarkably reduced.In the method according to an example embodiment of the presentdisclosure, an undiluted solution of a liquid amine can be used withoutusing a solvent, and, thus, a very high productivity can be obtained ina relatively small reactor as compared with a case where a solvent isused. Further, remaining impurities contained in a liquid aminederivative can be minimized, and, thus, very pure solid powder of acarbamic acid derivative with few impurities or with substantially noimpurities can be prepared.

In particular, the solid powder of the carbamic acid derivative preparedaccording to an example embodiment of the present disclosure exists instable solid state at room temperature as compared with the liquid aminederivative. Thus, (1) an amine vapor is not produced so that the solidpowder of the carbamic acid derivative is odorless; (2) the solid powderof the carbamic acid derivative is not easily oxidized in the air sothat it is easy and safe to handle and use it; (3) the solid powder ofthe carbamic acid derivative can be easily separated into the amine andthe carbon dioxide during the reaction so that it has a reactivityequivalent to that of the liquid amine derivative; (4) the solid powderof the carbamic acid derivative can be used in conditions without asolvent; (5) the solid powder of the carbamic acid derivative does notcontain impurities, so that less by-products are produced through a sidereaction; (6) general toxicities of the liquid amine derivative tohumans are remarkably reduced; (7) the solid powder of the carbamic acidderivative is hardly inflammable; and (8) the solid powder of thecarbamic acid derivative contains few impurities, so that it can bereduced to an amine derivative having a very high purity.

The foregoing summary is illustrative only and is not intended to be inany way limiting. In addition to the illustrative aspects, embodiments,and features described above, further aspects, embodiments, and featureswill become apparent by reference to the drawings and the followingdetailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

In the detailed description that follows, embodiments are described asillustrations only since various changes and modifications will becomeapparent to those skilled in the art from the following detaileddescription. The use of the same reference numbers in different figuresindicates similar or identical items.

FIG. 1 provides a photo image of the solid powder of carbamic acidderivatives prepared in Example 1 and Examples 4 to 8 of the presentdisclosure.

DETAILED DESCRIPTION

Hereinafter, example embodiments will be described in detail withreference to the accompanying drawings so that inventive concept may bereadily implemented by those skilled in the art.

However, it is to be noted that the present disclosure is not limited tothe example embodiments but can be realized in various other ways. Inthe drawings, certain parts not directly relevant to the description areomitted to enhance the clarity of the drawings, and like referencenumerals denote like parts throughout the whole document.

Throughout the whole document of the present disclosure, the terms“connected to” or “coupled to” are used to designate a connection orcoupling of one element to another element and include both a case wherean element is “directly connected or coupled to” another element and acase where an element is “electronically connected or coupled to”another element via still another element.

Throughout the whole document of the present disclosure, the term “on”that is used to designate a position of one element with respect toanother element includes both a case that the one element is adjacent tothe another element and a case that any other element exists betweenthese two elements.

Throughout the whole document of the present disclosure, the term“comprises” or “includes” and/or “comprising” or “including” used in thedocument means that one or more other components, steps, operations,and/or the existence or addition of elements are not excluded inaddition to the described components, steps, operations and/or elements.

The terms “about”, “approximately” or “substantially” used in thisdocument are intended to have meanings close to numerical values orranges specified with an allowable error and intended to preventaccurate or absolute numerical values disclosed for understanding of thepresent invention from being illegally or unfairly used by anyunconscionable third party.

Throughout the whole document of the present disclosure, the term “stepof” does not mean “step for.”

Throughout the whole document of the present disclosure, the term“combinations thereof” included in Markush type description meansmixture or combinations thereof one or more components, steps,operations and/or elements selected from the group consisting ofcomponents, steps, operation and/or elements described in Markush typeand thereby means that the disclosure includes one or more components,steps, operations and/or elements selected from the Markush group.

Throughout the whole document of the present disclosure, the description“A and/or B” means “A or B, or A and B.”

Throughout the whole document of the present disclosure, the term “alkylgroup” may include linear or branched, saturated or unsaturated C₁₋₃₀alkyl groups and may include, for example methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl,eicosanyl, or all available isomers thereof, but the present disclosuremay not be limited thereto.

Hereinafter, example embodiments of the present disclosure will beexplained in detail, but the present disclosure may not be limitedthereto.

In accordance with an aspect of the present disclosure, there isprovided a preparation method for solid powder of a carbamic acidderivative, including: reacting an amine derivative with carbon dioxideat a temperature in a range of from about −30° C. to about 500° C. andat a pressure in a range of from about 0.3 MPa to about 100 MPa.

In accordance with an example embodiment of the present disclosure, theamine derivative may include an amine-based compound represented by thefollowing Chemical Formula 1 or Chemical Formula 2, but may not belimited thereto:

-   -   wherein in Chemical Formulas 1 or 2,    -   each of R₁, R₂, R₃ and R₄ is independently hydrogen; a C₁₋₃₀        alkyl group substituted or non-substituted with nitrogen; a        phenyl group substituted or non-substituted with nitrogen; a        C₆₋₃₀ aryl group substituted or non-substituted with nitrogen;        or a C₃₋₃₀ cycloalkyl group substituted or non-substituted with        nitrogen, and    -   R₅ is a C₂₋₃₀ alkyl group substituted or non-substituted with        nitrogen; a phenyl group substituted or non-substituted with        nitrogen; a C₆₋₃₀ aryl group substituted or non-substituted with        nitrogen; or a C₃₋₃₀ cycloalkyl group substituted or        non-substituted with nitrogen.

In accordance with an example embodiment of the present disclosure, theamine-based compound may include at least one primary or secondary aminegroup, but may not be limited thereto.

In accordance with an example embodiment of the present disclosure, theamine-based compound may include a liquid amine, but may not be limitedthereto.

In accordance with an example embodiment of the present disclosure, theprepared carbamic acid derivative may include a compound represented bythe following Chemical Formula 3, Chemical Formula 3′, or ChemicalFormula 4, but may not be limited thereto:

-   -   wherein in Chemical Formulas 3, 3′, or 4,    -   each of R₁, R₂, R₃, and R₄ is independently hydrogen; a C₁₋₃₀        alkyl group substituted or non-substituted with nitrogen; a        phenyl group substituted or non-substituted with nitrogen; a        C₆₋₃₀ aryl group substituted or non-substituted with nitrogen;        or a C₃₋₃₀ cycloalkyl group substituted or non-substituted with        nitrogen, and    -   R₅ is a C₂₋₃₀ alkyl group substituted or non-substituted with        nitrogen; a phenyl group substituted or non-substituted with        nitrogen; a C₆₋₃₀ aryl group substituted or non-substituted with        nitrogen; or a C₃₋₃₀ cycloalkyl group substituted or        non-substituted with nitrogen.

The compound represented by Chemical Formula 3′ may be the same orsubstantially same as the compound represented by Chemical Formula 3.

In accordance with an example embodiment of the present disclosure, acontent of an amine group (—NH) in the amine derivative may be fromabout 5 wt % to about 99 wt %, but may not be limited thereto.

In accordance with an example embodiment of the present disclosure, thetemperature may be in a range of from about −30° C. to about 500° C.,but may not be limited thereto. During the reaction, if the temperatureis too low or too high, a system or costs may be unnecessarily consumedto maintain a low temperature or a high temperature. By way of example,the temperature may be in a range of from about −30° C. to about 500°C., from about −30° C. to about 400° C., from about −30° C. to about300° C., from about −30° C. to about 200° C., from about −30° C. toabout 100° C., from about −30° C. to about 50° C., from about −30° C. toabout 30° C., from about −30° C. to about 20° C., from about −30° C. toabout 10° C., from about −30° C. to about 0° C., from about −30° C. toabout −10° C., from about −30° C. to about −20° C., from about −20° C.to about 500° C., from about −10° C. to about 500° C., from about 0° C.to about 500° C., from about 10° C. to about 500° C., from about 20° C.to about 500° C., from about 30° C. to about 500° C., from about 50° C.to about 500° C., from about 100° C. to about 500° C., from about 200°C. to about 500° C., from about 300° C. to about 500° C., from about400° C. to about 500° C., or from about 0° C. to about 300° C., but thepresent disclosure may not be limited thereto.

In accordance with an example embodiment of the present disclosure, thepressure may be in a range of from about 0.3 MPa to about 100 MPa, butmay not be limited thereto. During the reaction, if the pressure is lessthan about 0.3 MPa, solid powder of a carbamic acid derivative may notbe formed and a gel type compound may be formed. By way of example, thepressure may be in a range of from about 0.3 MPa to about 100 MPa, fromabout 0.3 MPa to about 90 MPa, from about 0.3 MPa to about 80 MPa, fromabout 0.3 MPa to about 70 MPa, from about 0.3 MPa to about 60 MPa, fromabout 0.3 MPa to about 50 MPa, from about 0.3 MPa to about 40 MPa, fromabout 0.3 MPa to about 30 MPa, from about 0.3 MPa to about 20 MPa, fromabout 0.3 MPa to about 10 MPa, from about 0.3 MPa to about 5 MPa, fromabout 0.3 MPa to about 1 MPa, from about 1 MPa to about 100 MPa, fromabout 5 MPa to about 100 MPa, from about 10 MPa to about 100 MPa, fromabout 20 MPa to about 100 MPa, from about 30 MPa to about 100 MPa, fromabout 40 MPa to about 100 MPa, from about 50 MPa to about 100 MPa, fromabout 60 MPa to about 100 MPa, from about 70 MPa to about 100 MPa, fromabout 80 MPa to about 100 MPa, from about 90 MPa to about 100 MPa, orfrom about 1 MPa to about 50 MPa, but the present disclosure may not belimited thereto.

The reaction may be made by adding the carbon dioxide to the aminederivative, and even when the carbon dioxide is added to an additionalsolvent besides the amine derivative, pure solid powder of a carbamicacid derivative can be prepared in an equivalent manner to a case wherethe amine derivative reacts with the carbon dioxide without a solvent.

In accordance with an example embodiment of the present disclosure, thepreparation method for solid powder of the carbamic acid derivative mayinclude reacting a mixed solution of the amine derivative and one ormore selected from the group consisting of ethers, alcohols, aliphatichydrocarbons, carbocycles, heterocycles, aromatics, substitutedheteroaromatic cycles, and so on, with the carbon dioxide, but may notbe limited thereto. As described above, if an additional solvent isinput besides the amine derivative, a content of the amine derivative inthe mixed solution may be from about 1 wt % to about 99 wt %, forexample, from about 1 wt % to about 99 wt %, from about 1 wt % to about90 wt %, from about 1 wt % to about 80 wt %, from about 1 wt % to about70 wt %, from about 1 wt % to about 60 wt %, from about 1 wt % to about50 wt %, from about 1 wt % to about 40 wt %, from about 1 wt % to about30 wt %, from about 1 wt % to about 20 wt %, from about 1 wt % to about10 wt %, from about 1 wt % to about 5 wt %, from about 5 wt % to about99 wt %, from about 10 wt % to about 99 wt %, from about 20 wt % toabout 99 wt %, from about 30 wt % to about 99 wt %, from about 40 wt %to about 99 wt %, from about 50 wt % to about 99 wt %, from about 60 wt% to about 99 wt %, from about 70 wt % to about 99 wt %, from about 80wt % to about 99 wt %, or from about 90 wt % to about 99 wt %, but thepresent disclosure may not be limited thereto.

In accordance with an example embodiment of the present disclosure, inthe preparation method for the solid powder of the carbamic acidderivative, the method may further include, after the reaction with thecarbon dioxide, reducing the pressure to be in a range of from about0.01 MPa to about 0.1 MPa so as to evaporate excess carbon dioxide, butthe present disclosure may not be limited thereto.

In accordance with an example embodiment of the present disclosure, inthe preparation method for solid powder of the carbamic acid derivative,the method may further include washing the prepared solid powder of thecarbamic acid derivative by using C₁-C₁₂ alcohols, tetrahydrofuran,ethers, dimethylformamide, or mixed solutions thereof, and drying thesolid powder of the carbamic acid derivative, but the present disclosuremay not be limited thereto. If the method further includes the washingand drying step, impurities in the amine derivative are removed andsolid powder of the carbamic acid derivative having a high purity can beprepared.

In accordance with an example embodiment of the present disclosure, thecarbon dioxide may include carbon dioxide in a gas-phase, carbon dioxidein a liquid-phase, carbon dioxide in a supercritical state, orsolid-phase dry ice, but the present disclosure may not be limitedthereto.

In accordance with another aspect of the present disclosure, there isprovided a reduction method for solid powder of a carbamic acidderivative, the method including: dissolving the solid powder of thecarbamic acid derivative prepared by the method of the above-describedaspect of the present disclosure in a solvent; refluxing the carbamicacid derivative in the solvent at a temperature in a range of from about30° C. to about 100° C.; and evaporating the solvent to obtain an aminederivative and carbon dioxide.

In accordance with an example embodiment of the present disclosure, thesolvent is not particularly limited as long as it can dissolve asolid-state carbamic acid derivative and can be easily separated fromthe prepared amine derivative and may include, for example,C₁-C₁₂alcohols, C₂-C₁₂ ethers, and the like, but may not be limitedthereto.

In accordance with an example embodiment of the present disclosure, thetemperature may be in a range of from about 30° C. to about 100° C.,from about 30° C. to about 90° C., from about 30° C. to about 80° C.,from about 30° C. to about 70° C., from about 30° C. to about 60° C.,from about 30° C. to about 50° C., from about 30° C. to about 40° C.,from about 40° C. to about 100° C., from about 50° C. to about 100° C.,from about 60° C. to about 100° C., from about 70° C. to about 100° C.,from about 80° C. to about 100° C., from about 90° C. to about 100° C.,or from about 50° C. to about 80° C., but the present disclosure may notbe limited thereto.

In accordance with another aspect of the present disclosure, there isprovided a preparation method for an imine compound, the methodincluding: reacting the solid powder of the carbamic acid derivativeprepared by the preparation method of the above-described aspect of thepresent disclosure with an aldehyde to obtain an imine compound.

In accordance with an example embodiment of the present disclosure, thesolid powder of the carbamic acid derivative may include a compoundrepresented by the following Chemical Formula 3, Chemical Formula 3′, orChemical Formula 4, but may not be limited thereto:

-   -   wherein in Chemical Formulas 3, 3′, or 4,    -   each of R₁, R₂, R₃ and R₄ is independently hydrogen; a C₁₋₃₀        alkyl group substituted or non-substituted with nitrogen; a        phenyl group substituted or non-substituted with nitrogen; a        C₆₋₃₀ aryl group substituted or non-substituted with nitrogen;        or a C₃₋₃₀ cycloalkyl group substituted or non-substituted with        nitrogen, and    -   R₅ is a C₂₋₃₀ alkyl group substituted or non-substituted with        nitrogen; a phenyl group substituted or non-substituted with        nitrogen; a C₆₋₃₀ aryl group substituted or non-substituted with        nitrogen; or a C₃₋₃₀ cycloalkyl group substituted or        non-substituted with nitrogen.

The compound represented by Chemical Formula 3′ may be the same orsubstantially same as the compound represented by Chemical Formula 3.

In accordance with an example embodiment of the present disclosure, anycompound containing an aldehyde group may be used for the aldehydewithout limitation. For, example, the aldehyde may include a C₁-C₁₂compound containing an aldehyde group such as an C₁-C₁₂ alkyl aldehyde,or an C₆-C₁₂ arylaldehyde without limitation.

In accordance with an example embodiment of the present disclosure, thereaction between the solid powder of the carbamic acid derivative andthe aldehyde may be carried out with no solvent or in the presence of asolvent.

In accordance with an example embodiment of the present disclosure, asthe solvent in the reaction of the solid powder of the carbamic acidderivative and the aldehyde, any solvent, which can dissolve asolid-state carbamic acid derivative and be easily separated from animine compound to be prepared, may be used without limitation, and forexample, the solvent may include C₁-C₁₂ alcohols, or C₂-C₁₂ ethers andothers, but not be limited thereto.

In accordance with an example embodiment of the present disclosure, thetemperature may be in a range of from about 30° C. to about 100° C.,from about 30° C. to about 90° C., from about 30° C. to about 80° C.,from about 30° C. to about 70° C., from about 30° C. to about 60° C.,from about 30° C. to about 50° C., from about 30° C. to about 40° C.,from about 40° C. to about 100° C., from about 50° C. to about 100° C.,from about 60° C. to about 100° C., from about 70° C. to about 100° C.,from about 80° C. to about 100° C., from about 90° C. to about 100° C.,or from about 50° C. to about 80° C., but may not be limited thereto.

Hereinafter, the present invention will be explained in detail withreference to examples. However, it is clear that the following examplesare provided to illustrate the present invention but not to limit thepresent invention.

EXAMPLES Example 1

3 g (50.0 mmol) of ehtylenediamine (H₂NCH₂CH₂NH₂) was put into ahigh-pressure reactor (Parr 4714) with a volume of 45 mL without asolvent and reacted at a carbon dioxide pressure of 3 MPa at atemperature of 50° C. for 5 hours so as to obtain a solidehtylenediamine derivative. By putting the high-pressure reactor in anoil bath, the temperature was adjusted. After the reaction, remainingcarbon dioxide was removed, and a remaining solid was washed by using 20mL of ethanol and 20 mL of diethylether about five times and dried in avacuum for about 3 hours so as to obtain solid powder of a carbamic acidderivative.

In order to confirm characteristics of the obtained solid powder,elemental analysis and nuclear magnetic resonance (NMR) spectroscopyanalysis were carried out. According to results of the elementalanalysis and the nuclear magnetic resonance spectroscopy analysis, itwas confirmed that the obtained solid powder was a 2-aminoethyl carbamicacid compound represented as a chemical formula of H₃N⁺CH₂CH₂NHCOO⁻. Ayield of the obtained H₃N⁺CH₂CH₂NHCOO⁻ was 98% or more based on the usedehtylenediamine.

The results of the elemental analysis (unit: %) and the ¹H NMR analysison the H₃N⁺CH₂CH₂NHCOO⁻ as a product were as follows:

-   -   Elemental analysis (calculated value, experimental value): C        (34.61, 34.68), H (7.75, 7.71), N (26.91, 26.93);    -   ¹H NMR (400 MHz, CD₃OD, 27° C.) δ=4.659 (s, 3 H, —NH₃), 3.005        (t, 2 H, —CH₂NHCOO—), 2.765 (t, 2 H, —CH₂NH₃), 2.681 (s, 1 H,        —NH).

Comparative Example 1

Comparative Example 1 was carried out in the same manner as Example 1except that 3 g (50.0 mmol) of ehtylenediamine was used and carbondioxide was bubbled under atmospheric pressure at a temperature of 0° C.for 16 hours.

In this case, the ehtylenediamine was converted into a transparent geltype compound having a very high viscosity, but solids were notproduced. This result is the same as disclosed in U.S. Pat. No.3,551,226, and it is determined that not a single pure product but amixed unpure product was synthesized.

Example 2

Example 2 was carried out in the same manner as Example 1 except thatdiethylether (2 mL) was used as a solvent and 2 g (33.3 mmol) ofehtylenediamine was used so as to obtain solid powder of a carbamic acidderivative. In order to confirm characteristics of the obtained solidpowder of the carbamic acid derivative, an elemental analysis and anuclear magnetic resonance spectroscopy analysis were carried out in thesame manner as Example 1.

A result of the elemental analysis (unit: %) on the obtained solidpowder was almost the same as that of Example 1, and a result of the ¹HNMR analysis was exactly the same as that of Example 1. A yield of aproduct was 98% or more based on the used ehtylenediamine. According tothe results of the elemental analysis and the ¹H NMR analysis, it wasconfirmed that the powder prepared in Example 2 was H₃N⁺CH₂CH₂NHCOO⁻ asthe same material as that of Example 1.

Example 3

Example 3 was carried out in the same manner as Example 1 except that 10g of solid-phase carbon dioxide (dry ice) was used as a source of carbondioxide instead of gas-phase carbon dioxide and reacted withehtylenediamine so as to obtain solid powder of a carbamic acidderivative. In order to confirm characteristics of the obtained solidpowder of the carbamic acid derivative, an elemental analysis and anuclear magnetic resonance spectroscopy analysis were carried out in thesame manner as Example 1.

According to the results of the elemental analysis and the ¹H NMRanalysis on the obtained solid powder, it was confirmed that the powderprepared in Example 3 was H₃N⁺CH₂CH₂NHCOO⁻ as the same material as thatof Example 1.

Example 4

Example 4 was carried out in the same manner as Example 1 except that ata temperature of 25° C., 3 g (52.5 mmol) of allylamine (CH₂═CHCH₂NH₂)was used as a reactant instead of ehtylenediamine so as to obtain solidpowder of a carbamic acid derivative. In order to confirmcharacteristics of the obtained solid powder of the carbamic acidderivative, an elemental analysis was carried out in the same manner asExample 1.

According to the results of the elemental analysis and a massspectrometric analysis, it was confirmed that the obtained solid powderwas prop-2-en-1-aminium allylcarbamate [(CH₂═CHCH₂NH₂)₂CO₂ orCH₂═CHCH₂NH—CO₂ ⁻H₃N⁺CH₂CH═CH₂]. A yield of the obtained solid powderwas 96% or more based on the used allylamine.

The result of the elemental analysis (unit: %) was as follows:

-   -   Elemental analysis (calculated value, experimental value): C        (53.14, 53.09), H (8.92, 8.97), N (17.71, 17.65).

Example 5

Example 5 was carried out in the same manner as Example 1 except that 3g (28.0 mmol) of benzylamine (C₆H₅CH₂NH₂) was used as a reactant insteadof ehtylenediamine so as to obtain solid powder of a carbamic acidderivative. In order to confirm characteristics of the obtained solidpowder of the carbamic acid derivative, an elemental analysis wascarried out in the same manner as Example 1.

According to the results of the elemental analysis and a massspectrometric analysis, it was confirmed that the obtained solid powderwas phenylmethanaminium benzylcarbamate [(C₆H₅CH₂NH₂)₂CO₂ orC₆H₅CH₂NH—CO₂ ⁻H₃N⁺CH₂C₆H₅]. A yield of the obtained solid powder was98% or more based on the used benzylamine.

The result of the elemental analysis (unit: %) was as follows:

-   -   Elemental analysis (calculated value, experimental value): C        (69.74, 69.91), H (7.02, 7.18), N (10.85, 10.82).

Example 6

Example 6 was carried out in the same manner as Example 1 except that 3g (15.2 mmol) of dibenzylamine [(C₆H₅CH₂)₂NH] was used as a reactantinstead of ehtylenediamine so as to obtain solid powder of a carbamicacid derivative. In order to confirm characteristics of the obtainedsolid powder of the carbamic acid derivative, an elemental analysis wascarried out in the same manner as Example 1.

According to the results of the elemental analysis and a massspectrometric analysis, it was confirmed that the obtained solid powderwas dibenzylammonium dibenzylcarbamate [{(C₆H₅CH₂)₂NH}₂CO₂ or(C₆H₅CH₂)₂NH—CO₂ ⁻H₂N⁺(CH₂C₆H₅)₂]. A yield of the obtained solid powderwas 98% or more based on the used dibenzylamine.

The result of the elemental analysis (unit: %) was as follows:

-   -   Elemental analysis (calculated value, experimental value): C        (79.42, 79.45), H (6.90, 7.08), N (6.39, 6.43).

Example 7

Example 7 was carried out in the same manner as Example 1 except that 3g (14.9 mmol) of 1,4-(bis-aminopropyl)piperazine was used as a reactantinstead of ehtylenediamine so as to obtain solid powder of a carbamicacid derivative. In order to confirm characteristics of the obtainedsolid powder of the carbamic acid derivative, an elemental analysis wascarried out in the same manner as Example 1.

According to the results of the elemental analysis and a massspectrometric analysis, it was confirmed that the obtained solid powderwas 3-(4-(4-(carboxyamino)butyl)piperazin-1-yl)propan-1-aminium. A yieldof the obtained solid powder was 98% or more based on the used1,4-(bis-aminopropyl)piperazine.

The result of the elemental analysis (unit: %) was as follows:

-   -   Elemental analysis (calculated value, experimental value): C        (54.07, 54.37), H (9.90, 10.10), N (22.94, 23.18).

Example 8

Example 8 was carried out in the same manner as Example 1 except that 3g (24.7 mmol) of phenylethylamine (C₆H₅CH₂CH₂NH₂) was used as a reactantinstead of ehtylenediamine so as to obtain solid powder of a carbamicacid derivative. In order to confirm characteristics of the obtainedsolid powder of the carbamic acid derivative, an elemental analysis wascarried out in the same manner as Example 1.

According to the results of the elemental analysis and a massspectrometric analysis, it was confirmed that the obtained solid powderwas 2-phenylethanaminium phenethylcarbamate. A yield of the obtainedsolid powder was 98% or more based on the used phenyl ethyl amine.

The result of the elemental analysis (unit: %) was as follows:

-   -   Elemental analysis (calculated value, experimental value): C        (71.30, 71.21), H (7.74, 7.82), N (11.17, 10.98).

Example 9

Example 9 was carried out in the same manner as Example 1 except that 3g (41.0 mmol) of diethylamine [(CH₃CH₂)₂NH] was used as a reactantinstead of ehtylenediamine so as to obtain solid powder of a carbamicacid derivative. In order to confirm characteristics of the obtainedsolid powder of the carbamic acid derivative, an elemental analysis wascarried out in the same manner as Example 1.

According to the results of the elemental analysis and a massspectrometric analysis, it was confirmed that the obtained solid powderwas diethylammonium diethylcarbamate. A yield of the obtained solidpowder was 93% or more based on the used diethylamine.

The result of the elemental analysis (unit: %) was as follows:

-   -   Elemental analysis (calculated value, experimental value): C        (56.80, 57.01), H (11.65, 11.81), N (16.82, 17.01).

A structure, a reaction time, and a yield of the solid powder of thesolid carbamic acid derivatives produced from Examples 1 to 9 byreacting the amine with the carbon dioxides were as shown in thefollowing Table 1.

TABLE 1 Temp- erature^(a) Pressure Yield^(b) Amine derivative Carbamicacid derivative (° C.) (MPa) (%) Remarks Example 1

50 3 >98 white powder Comparative Example 1^(c)

— 0 0.1 — Example 2^(d)

50 3 >98 white powder Example 3^(e)

50 3 >98 white powder Example 4

25 3 >98 white powder Example 5

50 3 >98 needle crystal Example 6

50 3 >98 needle crystal Example 7

50 3 >98 white crystalline Example 8

50 3 >98 white crystalline powder Example 9

50 3 >95 white powder^(f) ^(a)Reaction time: 5 h, P_(CO2) = 3 MPa^(b)Isolation yield, no purification, based on amine ^(c)CO₂: bubbling(1 atm) ^(d)Di-ethyl ether: 2 mL ^(e)Dry ice: 10 g ^(f)Isolated at <10°C., unstable at >10° C.

Further, a photo image of the carbamic acid derivatives in solid powderform prepared in Example 1 and Examples 4 to 8 is shown in FIG. 1. Asshown in FIG. 1, it was confirmed that a carbamic acid derivative insolid powder form is prepared according to the preparation method forsolid powder of the carbamic acid derivative.

As described above, a solid-state carbamic acid derivative wassynthesized from a liquid amine derivative. The following Examples 10 to13 are examples showing that the solid powder of the carbamic acidderivatives prepared in Examples 1 to 9 had reactivities equivalent tothat of a liquid amine derivative.

Example 10 Reduction of Solid Powder of the Carbamic Acid Derivative toLiquid Amine Derivative

1 g of 3-(4-(4-(carboxyamino)butyl)piperazin-1-yl)propan-1-aminium asthe solid powder of the carbamic acid derivative prepared in Example 7was dissolved in 3 mL of methanol as a solvent and refluxed at atemperature of from 65° C. to 70° C. for 2 hours. Then, a remainingsolution was removed by depressurizing a pressure to 0.1 MPa at 0° C.and distilling the methanol so as to obtain a liquid compound. In orderto confirm characteristics of the obtained liquid compound, an elementalanalysis and a NMR analysis were carried out in the same manner asExample 1.

According to the results of the ¹H NMR analysis and the elementalanalysis, it was confirmed that the obtained liquid compound was1,4-(bis-aminopropyl)piperazine which is the liquid amine derivativeused as the reactant in Example 7. A yield of the obtained liquidcompound was 98% or more based on the solid compound used in the presentExample, and a purity of the obtained liquid compound was 99.8% or more.

Example 11 Reduction of Solid Powder of the Carbamic Acid Derivative toLiquid Amine Derivative

1 g of diethylammonium diethylcarbamate as the solid powder of thecarbamic acid derivative prepared in Example 9 was dissolved in 3 mL ofmethanol as a solvent and refluxed at a temperature of from 60° C. to65° C. for 2 hours. Then, a remaining solution was distilled underreduced pressure to 0.1 MPa at 0° C. so as to obtain a liquid compound.In order to confirm characteristics of the obtained liquid compound, anelemental analysis and a NMR analysis were carried out in the samemanner as Example 1.

According to the results of the ¹H NMR analysis and the elementalanalysis, it was confirmed that the obtained liquid compound wasdiethylamine which is the liquid amine used as the reactant in Example9. A yield of the obtained liquid compound was 95% or more based on thesolid compound used in the present Example, and a purity of the obtainedliquid compound was 99.9% or more.

Example 12 Reaction Between Solid Powder of the Carbamic Acid Derivativeand Benzaldehyde

0.791 g (5 mmol) of prop-2-en-1-aminium allylcarbamate[(CH₂═CHCH₂NH₂)₂CO₂] as the solid powder of the carbamic acid derivativeprepared in Example 4 was dissolved in 30 mL of ether as a solvent andreacted with 1.06 g (10 mmol) of benzaldehyde (C₆H₅CHO) and distilledunder reduced pressure to 0.1 MPa so as to obtain a liquid compound. Inorder to confirm characteristics of the obtained liquid compound, a NMRanalysis was carried out in the same manner as Example 1.

According to the result of the ¹H NMR analysis, it was confirmed thatthe obtained liquid compound was N-benzylideneprop-2-en-1-amine. A yieldof the obtained liquid compound was 97% or more based on the solidcompound used in the present Example, and a purity of the obtainedliquid compound was about 99.5%.

The result of the ¹H NMR analysis was as follows:

-   -   ¹H NMR (400 MHz, CDCl₃, 27° C.) δ=8.28 (s, 1 H, CH═N), 7.76 (m,        2 H, phenyl), 7.40 (m, 3 H, phenyl), 6.07 (m, 1 H, CH═CH₂), 5.23        (dd, 1 H, CH_(2a)═), 5.14 (dd, 1 H, CH_(2b)═), 4.25 (dd, 2H,        CH₂—N).

Example 13 Reaction Between Solid Powder of the Carbamic Acid Derivativeand Benzaldehyde

Example 13 was carried out in the same manner as Example 12 except that0.57 g (10 mmol) of allylamine (CH₂═CHCH₂NH₂) was used instead of asolid carbamic acid derivative. After the reaction, a liquid compoundwas obtained through distillation under reduced pressure to 0.1 MPa. Inorder to confirm characteristics of the obtained liquid compound, a NMRanalysis was carried out in the same manner as Example 1.

The obtained liquid compound was the same as the compound obtained inExample 12. A yield of the obtained liquid compound was 97% or morebased on the allylamine used in the present Example, and a purity of theobtained liquid compound was about 99.3%.

The above description of the present disclosure is provided for thepurpose of illustration, and it would be understood by those skilled inthe art that various changes and modifications may be made withoutchanging technical conception and essential features of the presentdisclosure. Thus, it is clear that the above-described embodiments areillustrative in all aspects and do not limit the present disclosure. Forexample, each component described to be of a single type can beimplemented in a distributed manner. Likewise, components described tobe distributed can be implemented in a combined manner.

The scope of the inventive concept is defined by the following claimsand their equivalents rather than by the detailed description of theexample embodiments. It shall be understood that all modifications andembodiments conceived from the meaning and scope of the claims and theirequivalents are included in the scope of the inventive concept.

What is claimed is:
 1. A preparation method for solid powder of acarbamic acid derivative, the method comprising: reacting an aminederivative with carbon dioxide at a temperature in a range of from about−30° C. to about 500° C. and at a pressure in a range of from about 0.3MPa to about 100 MPa.
 2. The preparation method of claim 1, wherein theamine derivative includes an amine-based compound represented by thefollowing Chemical Formula 1 or Chemical Formula 2:

wherein in Chemical Formulas 1 or 2, each of R₁, R₂, R₃ and R₄ isindependently hydrogen; a C₁₋₃₀ alkyl group substituted ornon-substituted with nitrogen; a C₆₋₃₀ aryl group substituted ornon-substituted with nitrogen; or a C₃₋₃₀ cycloalkyl group substitutedor non-substituted with nitrogen, and R₅ is a C₂₋₃₀ alkyl groupsubstituted or non-substituted with nitrogen; a C₆₋₃₀ aryl groupsubstituted or non-substituted with nitrogen; or a C₃₋₃₀ cycloalkylgroup substituted or non-substituted with nitrogen.
 3. The preparationmethod of claim 1, wherein the prepared carbamic acid derivativeincludes a compound represented by the following Chemical Formula 3,Chemical Formula 3′, or Chemical Formula 4:

wherein in Chemical Formulas 3, 3′, or 4, each of R₁, R₂, R₃ and R₄ isindependently hydrogen; a C_(l-30) alkyl group substituted ornon-substituted with nitrogen; a C₆₋₃₀ aryl group substituted ornon-substituted with nitrogen; or a C₃₋₃₀ cycloalkyl group substitutedor non-substituted with nitrogen, and R₅ is a C₃₋₃₀ alkyl groupsubstituted or non-substituted with nitrogen; a C₆₋₃₀ aryl groupsubstituted or non-substituted with nitrogen; or a C₃₋₃₀ cycloalkylgroup substituted or non-substituted with nitrogen.
 4. The preparationmethod of claim 1, wherein the temperature is in a range of from about0° C. to about 300° C.
 5. The preparation method of claim 1, wherein thepressure is in a range of from about 1 MPa to about 50 MPa.
 6. Thepreparation method of claim 1, the method including reacting a mixedsolution of the amine derivative and one or more selected from the groupconsisting of ethers, alcohols, aliphatic hydrocarbons, carbocycles,heterocycles, aromatics, and substituted heteroaromatic cycles, with thecarbon dioxide.
 7. The preparation method of claim 6, wherein a contentof the amine derivative in the mixed solution is from about 1 wt% toabout 99 wt%.
 8. The preparation method of claim 1, further comprising:after the reaction with the carbon dioxide, reducing the pressure to bein a range of from about 0.01 MPa to about 0.1 MPa so as to evaporateexcess carbon dioxide.
 9. The preparation method of claim 1, furthercomprising: washing the prepared solid powder of the carbamic acidderivative by using C₁-C₁₂ alcohols, tetrahydrofuran, ethers,dimethylformamide, or mixed solutions thereof, and drying the solidpowder of the carbamic acid derivative.
 10. The preparation method ofclaim 1, wherein the carbon dioxide includes carbon dioxide in agas-phase, carbon dioxide in a liquid-phase, carbon dioxide in asupercritical state, or solid-phase dry ice.